Process for preparing azo dyestuffs containing 2,4,6-tri-amino-3-(cyano ester or carbonamide)pyridine

ABSTRACT

Azo dyestuffs free of sulphonic acid groups and carboxylic acid groups are prepared by coupling a diazo compound with a coupler which is prepared by reacting an organic amine with a pyridinium salt having the formula ##STR1## IN WHICH R is substituted or unsubstituted alkyl, cycloalkyl, aralkyl or aryl; and 
     R 1  is substituted or unsubstituted alkyl or aralkyl. The dyestuffs are suitable for dyeing and printing synthetic materials such as polyolefines, polyvinyl compounds, cellulose acetate and triacetate and polyesters to give yellow to blue dyeings and prints with good fastness properties especially to light and sublimation.

This application is a continuation-in-part of U.S. application Ser. No. 442,621, filed Feb. 14, 1974, now U.S. Pat. No. 4,006,128.

This invention relates to azo dyestuffs which are free of sulphonic acid groups and carboxylic acid groups. The dyestuffs are prepared by coupling a diazotized amine of the formula

    D--NH.sub.2                                                (II)

with a coupling component (IV) which is obtained by reacting a pyridinium salt of the formula (III) below with at least two equivalents of an organic amine at a temperature of 110° to 130° C. and optionally converting the cyano group into an ester or carbonamide group in the known manner.

The reaction of the pyridinium salt (III) with the amines is either carried out in excess amine or in the presence of an inert solvent such as, for example, chloroform, acetonitrile, tetrahydrofurane and others.

The pyridinium salt has the formula ##STR2## IN WHICH

R is substituted or unsubstituted alkyl, cycloalkyl, aralkyl, or aryl; and

R₁ is substituted or unsubstituted alkyl or aralkyl.

The pyridinium salts (III) are in part known from Angewandte Chemie 84, 1184 (1972) or obtainable according to the process described there.

The organic amine, for example, can have the formula

    R.sub.3 --NH.sub.2

in which

R₃ is substituted or unsubstituted alkyl, aralkyl or aryl, particularly C₁ -C₄ -alkyl which can be substituted by hydroxy, methoxy or ethoxy; benzyl or phenylethyl which can be substituted by chlorine, C₁ -C₄ -alkyl or C₁ -C₄ -alkoxy; phenyl or phenyl substituted by C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, halogen or cyano.

Suitable organic amines are primary C₁ -C₄ - alkylamines, arylamines and phenyl-C₁ -C₃ -alkylamines, such as, for example, methylamine, ethylamine, n-propylamine, n-butylamine, β-hydroxyethylamine, aniline, benzylamine, phenylethylamine, γ-hydroxypropylamine, γ-ethoxypropylamine, β-methoxyethylamine and γ-methoxypropylamine.

As already indicated, the cyano group in the coupling component can be optionally converted to an ester or a carbonamide group in the known manner.

The carbonamide group can be represented by the formula ##STR3## in which

Q₁ and Q₂ independently of one another are hydrogen, alkyl, cycloalkyl, aralkyl or aryl; or conjointly with the nitrogen atom form a 5-membered or 6-membered heterocyclic structure; for example a morpholine, piperidine or pyrrolidine ring.

The ester group can be represented by the formula

    --COOQ.sub.3

in which

Q₃ is alkyl or aralkyl.

Suitable radicals D in the diazotized amine (II) are aromatic-carbocyclic radicals, especially those of the benzene, diphenyl, naphthalene and anthraquinone series, and aromatic-heterocyclic radicals, preferably those of the thiadiazole, triazole, benztriazole, indole, benzthiazole and oxdiazole series.

Preferred radicals D are radicals of the benzene, thiadiazole and benzthiazole series. These radicals can possess further non-ionic substituents customary in dyestuff chemistry. As examples there may be mentioned: halogen atoms, such as chlorine, bromine and fluorine, alkyl, alkoxy aryl, aryloxy, nitro, cyano, trifluoromethyl, alkylcarbonyl, alkoxycarbonyl, arylcarbonyl, alkylsulphonyl, arylsulphonyl, alkylcarbonylamino, arylcarbonylamino, arylazo, sulphamoyl and carbamoyl radicals; alkyl and alkoxy are preferably to be understood as radicals of this type with 1-4 C atoms and aryl is preferably to be understood as phenyl radicals which are optionally substituted by halogen, C₁ -C₄ -alkyl and C₁ -C₄ -alkoxy.

The alkyl radicals R, R₁, Q₁, Q₂ and Q₃ preferably possess 1-6 C atoms and can be substituted, for example, by halogen, such as F, Cl or Br, or by cyano, hydroxyl, C₁ -C₄ -alkoxy or C₂ -C₅ -alkoxycarbonyl groups.

Cycloalkyl radicals R, Q₁ and Q₂ can preferably be cyclohexyl radicals which can be substituted by, for example, methyl radicals.

Suitable aryl radicals R, Q₁ and Q₂ are above all phenyl radicals which are optionally substituted by C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, halogen or cyano; halogen is preferably to be understood as chlorine. The phenyl and tolyl radical are preferred.

Suitable aralkyl radicals R, R₁, Q₁, Q₂ and Q₃ are preferably benzyl and phenylethyl radicals which can be substituted by, for example, chlorine, C₁ -C₄ -alkyl or C₁ -C₄ -alkoxy.

Particularly valuable dyestuffs are obtained by coupling a diazotized amine of having the formula ##STR4## in which

Y is halogen, nitro, cyano, CF₃, C₂ -C₅ -alkylcarbonylamino, C₁ -C₄ -alkylsulphonyl, C₂ -C₅ -alkoxycarbonyl, phenyl, ##STR5##

Z is hydrogen, methyl, C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, nitrile or halogen;

V₁ and V₂ independently of one another are hydrogen or C₁ -C₄ -alkyl; and

n is the number 1 or 2;

with a coupler (IV) prepared as indicated above in which the cyano group is unconverted or is converted to --CONQ₁ Q₂ ; and in which R and R₁ are C₁ -C₆ -alkyl, or C₁ -C₆ -alkyl substituted by OH, CN, halogen, C₁ -C₄ -alkoxy or C₂ -C₅ -alkylcarbonyl; and

Q₁ and Q₂ are hydrogen or C₁ -C₄ -alkyl.

The abovementioned C₁ -C₄ -alkyl radicals are n-propyl, n-butyl and above all methyl and ethyl radicals. Halogen is preferably to be understood as chlorine and bromine.

Among the C₂ -C₅ -alkoxycarbonyl radicals Y which have been mentioned, the methoxycarbonyl and ethoxycarbonyl radicals are to be regarded as particularly suitable. Acetyl is the preferred alkylcarbonyl group.

It has now been discovered that the reaction of an amine having the formula R₃ NH₂ with a pyridinium salt having the formula ##STR6## under the conditions described above is ##STR7## as incorrectly described in our parent application, Ser. No. 442,621.

Accordingly, the dyestuffs of this invention produced by the method described above are found to have the formula ##STR8## in which

D, R and R₁ and R₃ all have the meanings given above

and

X is cyano, or an ester or carbonamide group as defined above.

The coupling of the diazotized amines (II) with the compounds (IV) is carried out in a manner which is in itself known, in a weakly acid, neutral or weakly alkaline, aqueous or organic-aqueous medium, the addition of an acid-binding agent, such as, for example, sodium acetate, being advisable at times.

As examples of suitable diazo compounds of the formula (II) there may be mentioned: aniline, 2-, 3- and 4-N,N-dimethylamino-aniline, 2-, 3- and 4-aminotoluene, 3- and 4-amino-benzotrifluoride, 3- and 4-amino-1,2-dimethyl-benzene, 2-, 4- and 5-amino-1,3-dimethylbenzene, 4-amino-1,3,5-trimethylbenzene, 2-, 3- and 4-aminoanisole, 2-, 3- and 4-aminophenetole, 2-amino-1,4-dimethoxybenzene, 2-amino-1,4-diethoxybenzene, 2-, 3- and 4-chloroaniline, 2-, 3- and 4-bromoaniline, 2,3-, 2,4-, 2,5- and 3,4-dichloroaniline, 2,5-dibromoaniline, 2,4,5-, 2,4,6-, 3,4,5- and 3,4,6-trichloroaniline, 3-, 4-, 5- and 6-chloro-2-amino-toluene, 4-chloro-3-amino-toluene, 2-chloro-4-amino-toluene, 5-chloro-2-amino-benzotrifluoride, 4,5- and 4,6-dichloro-2-amino-toluene, 2,5- and 4,6-dichloro-3-amino-toluene, 2,5- and 3,5-dichloro-4-amino-toluene, 4,5,6-trichloro-2-amino-toluene, 4-chloro-2-amino-1,3-dimethylbenzene, 6-chloro-3-amino-anisole, 2-chloro-4-amino-anisole, 3-chloro-4-aminoanisole, 2-, 3- and 4-nitroaniline, 3-nitro-4-amino-toluene, 5-nitro-4-amino-1,3-dimethylbenzene, 6-nitro-3-amino-anisole, 3-nitro-4-amino-anisole, 5-nitro-2-aminophenetole, 2-nitro-4-amino-phenetole, 3-nitro-4-amino-phenetole, 5-nitro-2-amino-1,4-dimethoxy-benzene, 5-nitro-2-amino-1,4-diethoxy-benzene, 2-chloro-4-nitroaniline, 2-bromo-4-nitroaniline, 4-chloro-2-nitroaniline, 4-bromo-2-nitroaniline, 2,6-dichloro-4-nitroaniline, 2-chloro-6-bromo-4-nitroaniline, 2,6-dibromo-4-nitroaniline, 2,4-dinitroaniline, 6-chloro-2,4-dinitroaniline, 6-bromo-2,4-dinitroaniline, 2,4,6-trinitroaniline, 2-, 3- and 4-amino-benzonitrile, 1-amino-2-cyano-5-chlorobenzene, 2-cyano-4-nitroaniline, 4-cyano-3-nitroaniline, 2,5-dichloro-4-aminosulphonylaniline, 4-methylsulphonylaniline, 1-amino-2,4-dicyanobenzene, 1-amino-2,6-dicyano-4-nitrobenzene, 1-amino-2-chloro-4-methyl-sulphonylbenzene, 2-methylsulphonyl-4-nitroaniline, 4-methylsulphonyl-2-nitroaniline, 2-, 3- and 4-amino-benzaldehyde, 2-, 3- and 4-amino-acetophenone, 2-amino-5-nitro-acetophenone, 2-, 3- and 4-amino-benzophenone, 2-, 3- and 4-amino-4'-methyl-benzophenone, 2-, 3- and 4-amino-4'-methoxy-benzophenone, 4-amino-5-nitro-benzophenone, 2-, 3- and 4-amino-benzoic acid ethyl ester, 2-, 3- and 4-aminobenzoic acid n-butyl ester, 2-, 3- and 4-amino-benzoic acid cyclohexyl ester, 2-, 3- and 4-amino-benzoic acid amide, 2-, 3- and 4-amino-benzoic acid monomethylamide, 2-, 3- and 4-amino-benzoic acid dimethylamide, 2-, 3- and 4-amino-benzoic acid ethyleneimide, 2-, 3- and 4-amino-benzoic acid isopropylamide, 2-, 3- and 4-amino-benzoic acid diethylamide, 2-, 3- and 4-amino-benzoic acid di-n-butylamide, 2-, 3- and 4-aminobenzoic acid morpholide, 2-, 3- and 4-amino-benzoic acid anilide, 2-, 3- and 4-amino-benzoic acid N-methylanilide, 2-, 3- and 4-amino-phenyl acetic acid ester, 2-, 3- and 4-aminophenyl β-methoxy-propionic acid ester, 2-, 3- and 4-aminophenyl phenylacetic acid ester, 2-, 3- and 4-amino-phenyl phenoxyacetic acid ester, 2-, 3- and 4-amino-phenyl benzoic acid ester, 2-, 3- and 4-amino-phenyl methylsulphonic acid ester, 2-, 3- and 4-amino-phenyl ethylsulphonic acid ester, 2-, 3- and 4-amino-phenyl β-chloroethylsulphonic acid ester, 2-, 3- and 4-amino-phenyl butylsulphonic acid ester, 2-, 3- and 4-amino-phenyl n-hexylsulphonic acid ester, 2-, 3- and 4-amino-phenyl phenylsulphonic acid ester, 2-, 3- and 4-aminophenyl (4'-methyl-phenyl)-sulphonic acid ester, 2-, 3- and 4-amino-phenyl (4'-methoxy-phenyl)-sulphonic acid ester, 2-, 3- and 4-amino-phenyl β-ethoxy-ethylsulphamic acid ester, 2-, 3- and 4-amino-benzenesulphonic acid ethyl ester, 2-, 3- and 4-amino-benzenesulphonic acid phenyl ester, 2-, 3- and 4-amino-phenyl dimethylsulphamic acid ester, 2-, 3- and 4-amino-phenyl ethylsulphamic acid ester, 2-, 3- and 4-amino-phenyl diethylsulphamic acid ester, 2-, 3- and 4-amino-phenyl di-n-butylsulphamic acid ester, 2-, 3- and 4-amino-phenyl cyclohexylsulphamic acid ester, 2-, 3- and 4-amino-benzenesulphonic acid amide, 2-, 3- and 4-amino-benzenesulphonic acid monomethylamide, 2-, 3- and 4-aminobenzenesulphonic acid dimethylamide, 2-, 3- and 4-amino-benzenesulphonic acid ethyleneimide, 2-, 3- and 4-amino-benzenesulphonic acid diethylamide, 2-, 3- and 4-amino-benzenesulphonic acid di-n-butylamide, 2-, 3- and 4-amino-benzenesulphonic acid morpholide, 2-, 3- and 4-amino-benzenesulphonic acid cyclohexylamide, 2-, 3- and 4-amino-benzenesulphonic acid anilide, 2-, 3- and 4-amino-benzenesulphonic acid N-methyl-anilide, 1-methyl-2-amino-benzene-4-sulphonic acid amide, 1-methoxy-2-amino-benzene-4-sulphonic acid amide, 1-methoxy-2-amino-benzene-4-sulphonic acid N-methylanilide, 1-chloro-2-amino-benzene-4-sulphonic acid dimethylamide, 1-chloro-2-amino-benzene-5-sulphonic acid β-ethoxy-ethylamide, 1-chloro-3-amino-benzene-4-sulphonic acid amide, 1-chloro-4-amino-benzene-2-sulphonic acid dimethylamide, 4-amino-benzene-methylurethane, 2-, 3- and 4-amino-acetanilide, 2-, 3- and 4-amino-phenoxyacetanilide, 2-, 3- and 4-amino-N-methyl-acetanilide, 4-amino-diphenyl, 4-amino-diphenyl-4'-carboxylic acid ethyl ester, 4-amino-4'-acetylamino-diphenyl, 4-amino-2',4'-dinitro-diphenylamine, 4-amino-3-nitro-diphenylamine-4'-sulphonic acid amide, 1-amino-naphthalene, 1-amino-5-ethoxy-naphthalene, 2-chloro-1-amino-naphthalene, 2-amino-naphthalene, 2-amino-naphthalene-6-sulphonic acid dimethylamide, 5-nitro-2-amino-thiazole, 4-amino-azo-benzene, 2',3-dimethyl-4-amino-azo-benzene, 2-methyl-4-amino-5-methoxy-azo-benzene, phenyl-azo-4-aminonaphthalene, 4-methylsulphonylaniline, 2-aminothiazole, 2-amino-5-nitrothiazole, 2-amino-5-thiocyanatothiazole, 2-aminobenzthiazole, 2-amino-6-methoxybenzthiazole, 2-amino-6-ethoxybenzthiazole, 2-amino-6-chlorobenzthiazole, 2-amino-4,5-dichlorobenzthiazole, 2-amino-5,6-dichlorobenzthiazole, 3-amino-5-nitrobenzisothiazole and 3-phenyl-5-amino-thiadiazole-(1,2,4).

The new dyestuffs are very suitable for dyeing and printing structures of synthetic materials such as, for example, polyolefines, polyvinyl compounds, cellulose 21/2-acetate, cellulose triacetate and especially polyester materials, for example polyethylene glycol terephthalate. On these they give, by the customary dyeing and printing processes, yellow to blue dyeings and prints with good fastness properties, especially good fastness to light and sublimation.

The materials mentioned are appropriately dyed from aqueous suspension in the presence of carriers between about 80° C. and 110° C., in the absence of carriers between about 110° C. and 140° C., or by the thermofixing process at about 170° C. and 230° C. Printing can be carried out by steaming the printed goods in the presence of a carrier at temperatures between 80° C. and 100° C. or in the absence of a carrier at about 110° C. to 140° C. or treating them by the thermofixing process at about 170° C. and 230° C.

In the examples which follow, parts denote parts by weight and percentages denote percentages by weight.

EXAMPLE 1

23.3 parts of 1-methyl-2-chloro-3-cyano-4-methylamino-6-amino-pyridinium chloride (prepared according to the instructions of A. L. Cossey; Angewandte Chemie, 84 (1972) page 1185, and 100 parts of benzylamine are heated to 110°-130° C. for four to six hours. The reaction mixture is subsequently introduced, while still hot, into approximately 500 parts of ice water. The product which precipitates is filtered off, thoroughly washed with water and dried. Approximately 24 parts of the compound of the formula ##STR9## are obtained; the compound melts, after recrystallization from ethanol, at 148°-153° C. and contains small quantities of a pyridone impurity, produced by hydrolysis.

The table which follows indicates further dyestuffs according to the present invention and the colour shades of dyeings or prints which are obtainable therewith on polyester materials and which also possess good fastness properties.

    __________________________________________________________________________       Diazotized Amine    Coupled with the reaction product of                                                                 ##STR10##                             (DNH.sub.2)       amine (R.sub.3 NH.sub.2) reacted with                                                                Colour shade                        No.      D           R.sub.3         R  R.sub.1                                                                           on polyester                        __________________________________________________________________________     2.  4-Chlorophenyl   CH.sub.3        CH.sub.3                                                                          CH.sub.3                                                                          yellow                              3.  2,5-Dichlorophenyl                                                                              CH.sub.3        CH.sub.3                                                                          "  yellow                              4.  4-Phenylazophenyl                                                                               C.sub.2 H.sub.5 CH.sub.3                                                                          "  orange                              5.  2,5-Dichlorophenyl                                                                              C.sub.3 H.sub.7 CH.sub.3                                                                          "  yellow                              6.  4-Phenylazophenyl                                                          n-C.sub.4 H.sub.9                                                                  CH.sub.3         "               orange                                    7.  4-Chlorophenyl   C.sub.6 H.sub.5 CH.sub.3                                                                          "  yellow                              8.  2,5-Dichlorophenyl                                                                              "               CH.sub.3                                                                          "  yellow                              9.  2-Chloro-4-nitrophenyl                                                                          "               CH.sub.3                                                                          "  orange                              10. 4-Cyanophenyl    "               CH.sub.3                                                                          "  yellow                              11. 4-Carboethoxyphenyl                                                                             "               CH.sub.3                                                                          "  yellow                              12. 4-Methylphenyl   "               CH.sub.3                                                                          "  yellow                              13. 4-Phenylazophenyl                                                                               "               CH.sub.3                                                                          "  orange                              14. 3-Chlorophenyl   CH.sub.2C.sub.6 H.sub.5                                                                        CH.sub.3                                                                          "  yellow                              15. 4-Chlorophenyl   "               CH.sub.3                                                                          "  yellow                              16. 3,5-Dichlorophenyl                                                                              "               CH.sub.3                                                                          "  yellow                              17. 2,4-Dichlorophenyl                                                                              "               CH.sub.3                                                                          "  yellow                              18. 3-Methylphenyl   "               CH.sub.3                                                                          "  yellow                              19. 4-Methylphenyl   "               CH.sub.3                                                                          "  yellow                              20. 3-Trifluoromethylphenyl                                                                         "               CH.sub.3                                                                          "  yellow                              21. 4-Methoxyphenyl  "               CH.sub.3                                                                          "  yellow                              22. 2-Chloro-4-methylphenyl                                                                         "               CH.sub.3                                                                          "  yellow                              23. 2-Trifluoromethyl-5-chlorophenyl                                                                "               CH.sub.3                                                                          "  yellow                              24. 2-Chloro-5-methoxyphenyl                                                                        "               CH.sub.3                                                                          "  yellow                              25. 2-Chloro-4-nitrophenyl                                                                          "               CH.sub.3                                                                          "  orange                              26. 2-Cyanophenyl    "               CH.sub.3                                                                          "  yellow                              27. 4-Cyanophenyl    "               CH.sub.3                                                                          "  yellow                              28. 2-Cyano-5-chlorophenyl                                                                          "               CH.sub.3                                                                          "  yellow                              29. 2-Cyano-4-nitrophenyl                                                                           "               CH.sub.3                                                                          "  orange                              30. 2,4-Dicyanophenyl                                                                               "               CH.sub.3                                                                          "  yellow                              31. 3,4-Dicyanophenyl                                                                               "               CH.sub.3                                                                          "  yellow                              32. 4-Methylsulphonylphenyl                                                                         "               CH.sub.3                                                                          "  yellow                              33. 4-Acetylphenyl   "               CH.sub.3                                                                          "  yellow                              34. 4-Carboethoxyphenyl                                                                             "               CH.sub.3                                                                          "  yellow                              35. 4-Acetaminophenyl                                                                               "               CH.sub.3                                                                          "  yellow                              36. 4-Carbonamidophenyl                                                                             "               CH.sub.3                                                                          "  yellow                              37. 3-Sulphonamidophenyl                                                                            "               CH.sub.3                                                                          "  yellow                              38. 4-Sulphonamidophenyl                                                                            "               CH.sub.3                                                                          "  yellow                              39. 4-Sulphamidoxyphenyl                                                                            "               CH.sub.3                                                                          "  yellow                              40. 3-Sulphamidoxyphenyl                                                                            "               CH.sub.3                                                                          "  yellow                              41. 3-N,N-Diethylsulphamidoxyphenyl                                                                 "               CH.sub.3                                                                          "  yellow                              42. 3-Nitrophenyl    "               CH.sub.3                                                                          "  yellow                              43. 2-Nitro-4-cyclohexylphenyl                                                                      "               CH.sub.3                                                                          "  orange                              44. 4-Phenylaminophenyl                                                                             "               CH.sub.3                                                                          "  yellow                              45. Naphthyl-1       "               CH.sub.3                                                                          "  yellow                              46. Naphthyl-2       "               CH.sub.3                                                                          "  yellow                              47. 4-Phenylazophenyl                                                                               "               CH.sub.3                                                                          "  orange                              48. 4-Phenylazonaphthyl-1                                                                           "               CH.sub.3                                                                          "  red                                 49. 5-Nitro-thiazolyl-2                                                                             "               CH.sub.3                                                                          "  red                                 50. 6-Chloro-benzthiazolyl-2                                                                        "               CH.sub.3                                                                          "  red                                 51. 4-Chlorophenyl   "               C.sub.2 H.sub.5                                                                   C.sub.2 H.sub.5                                                                   yellow                              52. 2,5-Dichlorophenyl                                                                              "               C.sub.2 H.sub.5                                                                   "  yellow                              53. 4-Phenylazophenyl                                                                               "               C.sub.2 H.sub.5                                                                   "  orange                              54. 2,5-Dichlorophenyl                                                                              "               C.sub.6 H.sub.5                                                                   C.sub.6 H.sub.5                                                                   yellow                              55. 4-Phenylazophenyl                                                                               "               C.sub.6 H.sub.5                                                                   "  orange                              56. 2,5-Dichlorophenyl                                                                               ##STR11##      CH.sub.3                                                                          CH.sub.3                                                                          yellow                              57. 4-Phenylazophenyl                                                                               "               CH.sub.3                                                                          "  orange                              58. "                                                                                                ##STR12##      CH.sub.3                                                                          "  orange                              59. "                                                                                                ##STR13##      CH.sub.3                                                                          "  orange                              60. 2,5-Dichlorophenyl                                                                              CH.sub.2 CH.sub.2C.sub.6 H.sub.5                                                               CH.sub.3                                                                          "  yellow                              61. 4-Phenylazophenyl                                                                               "               CH.sub.3                                                                          "  orange                              62. 2,5-Dichlorophenyl                                                                              CH.sub.2CH.sub.2OH                                                                             CH.sub.3                                                                          "  yellow                              63. 2,5-Dichlorophenyl                                                                              CH.sub.2CH.sub.2OCH.sub.3                                                                      CH.sub.3                                                                          "  yellow                              64. "                CH.sub.2CH.sub.2CN                                                                             CH.sub.3                                                                          "  yellow                              65. "                CH.sub.2C.sub.6 H.sub.5                                                                        CH.sub.3                                                                          C.sub.2 H.sub.5                                                                   yellow                              66. "                CH.sub.2C.sub.6 H.sub.5                                                                        C.sub.2 H.sub.5                                                                   CH.sub.3                                                                          yellow                              67. 4-Phenylazophenyl                                                                               CH.sub.2C.sub.6 H.sub.5                                                                        C.sub.2 H.sub.5                                                                   "  orange                              68. 2,5-Dichlorophenyl                                                                              C.sub.6 H.sub.5 C.sub.2 H.sub.5                                                                   CH.sub.3                                                                          yellow                              69. "                C.sub.6 H.sub.5 C.sub.6 H.sub.5                                                                   C.sub.6 H.sub.5                                                                   yellow                              70. "                CH.sub.2 CH.sub.2OCH.sub.3                                                                     CH.sub.3                                                                          C.sub.6 H.sub.5                                                                   yellow                              71. 4-Phenylazophenyl                                                                               "               CH.sub.3                                                                          "  orange                              72. "                CH.sub.2C.sub.6 H.sub.5                                                                        CH.sub.3                                                                          CH.sub.3                                                                          orange                              73. 2-Chloro-5-trifluoromethylphenyl                                                                CH.sub.2C.sub.6 H.sub.5                                                                        CH.sub.3                                                                          CH.sub.3                                                                          yellow                              74. 4-Cyclohexyloxycarbonylphenyl                                                                   "               CH.sub.3                                                                          "  yellow                              75. 2-Nitrophenyl    "               CH.sub.3                                                                          "  scarlet                             76. 4-Nitrophenyl    "               CH.sub.3                                                                          "  scarlet                             77. 2-Chloro-4-nitrophenyl                                                                          "               CH.sub.3                                                                          "  scarlet                             78. 2-Methoxy-4-nitrophenyl                                                                         "               CH.sub.3                                                                          "  red                                 79. 2-Cyano-4-nitrophenyl                                                                           "               CH.sub.3                                                                          "  red                                 80. 2-Methylsulphonyl-4-nitrophenyl                                                                 "               CH.sub.3                                                                          "  red                                 81. 2-Carbomethoxy-4-nitrophenyl                                                                    "               CH.sub.3                                                                          "  red                                 82. 2,5-Dimethoxy-4-nitrophenyl                                                                     "               CH.sub.3                                                                          "  red                                 83. Thiazolyl-2      "               CH.sub.3                                                                          "  orange                              84. 6-Methoxybenzthiazolyl-2                                                                        "               CH.sub.3                                                                          "  scarlet                             85. 5,6-Dichlorobenzthiazolyl-2                                                                     "               CH.sub.3                                                                          "  scarlet                             86. 2-Cyanophenyl    CH.sub.2CH.sub.2OH                                                                             CH.sub.3                                                                          "  yellow                              87. "                CH.sub.2CH.sub.2OCH.sub.3                                                                      CH.sub.3                                                                          "  yellow                              88. "                CH.sub.2CH.sub.2CH.sub.2OH                                                                     CH.sub.3                                                                          "  yellow                              89. "                CH.sub.2CH.sub.2CH.sub.2 OCH.sub.3                                                             CH.sub.3                                                                          "  yellow                              90. 4-Methylsulphonylphenyl                                                                         CH.sub.2CH.sub.2OH                                                                             CH.sub.3                                                                          "  yellow                              91. "                CH.sub.2CH.sub.2OCH.sub.3                                                                      CH.sub.3                                                                          "  yellow                              92. "                CH.sub.2CH.sub.2CH.sub.2OH                                                                     CH.sub.3                                                                          "  yellow                              93. 4-Methylsulphonylphenyl                                                                         CH.sub.2CH.sub.2CH.sub.2OCH.sub.3                                                              CH.sub.3                                                                          "  yellow                              94. "                CH.sub.2CH.sub.2CH.sub.2OC.sub.2 H.sub.5                                                       CH.sub.3                                                                          "  yellow                              95. "                                                                                                ##STR14##      CH.sub.3                                                                          "  yellow                              96. 4-Sulphonamidophenyl                                                                            CH.sub.2CH.sub.2OH                                                                             CH.sub.3                                                                          "  yellow                              97. 4-Sulphonamidophenyl                                                                            CH.sub.2CH.sub.2OCH.sub.3                                                                      CH.sub. 2                                                                         "  yellow                              98. "                CH.sub.2CH.sub.2CH.sub.2OH                                                                     CH.sub.3                                                                          "  yellow                              99. "                CH.sub.2CH.sub.2CH.sub.2OCH.sub.3                                                              CH.sub.3                                                                          "  yellow                              100.                                                                               "                CH.sub.2CH.sub.2CH.sub.2OC.sub.2 H.sub.5                                                       CH.sub.3                                                                          "  yellow                              101.                                                                               2,5-Dichloro-4-sulphonamidophenyl                                                               CH.sub.2C.sub.6 H.sub.5                                                                        CH.sub.3                                                                          "  golden yellow                       102.                                                                               "                CH.sub.2CH.sub.2OH                                                                             CH.sub.3                                                                          "  golden yellow                       103.                                                                               "                CH.sub.2CH.sub.2OCH.sub.3                                                                      CH.sub.3                                                                          "  golden yellow                       104.                                                                               "                CH.sub.2CH.sub.2CH.sub.2OH                                                                     CH.sub.3                                                                          "  golden yellow                       105.                                                                               "                CH.sub.2CH.sub.2CH.sub.2OCH.sub.3                                                              CH.sub.3                                                                          "  golden yellow                       106.                                                                               "                CH.sub.2CH.sub.2CH.sub.2OC.sub.2 H.sub.5                                                       CH.sub.3                                                                          "  golden yellow                       107.                                                                               2,5-Dichloro-4-benzylamino-                                                                     CH.sub.2CH.sub.2OCH.sub.3                                                                      CH.sub.3                                                                          "  golden yellow                           sulphonylphenyl                                                            108.                                                                               2,5-Dichloro-4-benzylamino-                                                                     CH.sub.2CH.sub.2CH.sub.2OC.sub.2 H.sub.5                                                       CH.sub.3                                                                          "  golden yellow                           sulphonylphenyl                                                            109.                                                                               2-Chloro-5-trifluoromethylphenyl                                                                CH.sub.2CH.sub.2OH                                                                             CH.sub.3                                                                          "  yellow                              110.                                                                               "                CH.sub.2CH.sub.2OCH.sub.3                                                                      CH.sub.3                                                                          "  yellow                              111.                                                                               "                                                                                                ##STR15##      CH.sub.3                                                                          "  yellow                              112.                                                                               "                CH.sub.2CH.sub.2CH.sub.2OH                                                                     CH.sub.3                                                                          "  yellow                              113.                                                                               "                CH.sub.2CH.sub.2CH.sub.2OCH.sub.3                                                              CH.sub.3                                                                          "  yellow                              114.                                                                               "                CH.sub.2CH.sub.2CH.sub.2OC.sub.2 H.sub.5                                                       CH.sub.3                                                                          "  yellow                              115.                                                                               4-Cyclohexyloxycarbonylphenyl                                                                   CH.sub.2CH.sub.2OH                                                                             CH.sub.3                                                                          "  yellow                              116.                                                                               "                CH.sub.2CH.sub.2OCH.sub.3                                                                      CH.sub.3                                                                          "  yellow                              117.                                                                               "                CH.sub.2CH.sub.2CH.sub.2OH                                                                     CH.sub.3                                                                          "  yellow                              118.                                                                               "                                                                                                ##STR16##      CH.sub.3                                                                          "  yellow                              119.                                                                               "                CH.sub.2CH.sub.2CH.sub.2OCH.sub.3                                                              CH.sub.3                                                                          "  yellow                              120.                                                                               2-Nitrophenyl    CH.sub.2CH.sub.2OH                                                                             CH.sub.3                                                                          "  scarlet                             121.                                                                               "                CH.sub.2CH.sub.2OCH.sub.3                                                                      CH.sub.3                                                                          "  scarlet                             122.                                                                               "                CH.sub.2CH.sub.2CH.sub.2OCH.sub.3                                                              CH.sub.3                                                                          "  scarlet                             123.                                                                               3-Nitrophenyl    CH.sub.2CH.sub.2OH                                                                             CH.sub.3                                                                          "  yellow                              124.                                                                               "                CH.sub.2CH.sub.2CH.sub.2OH                                                                     CH.sub.3                                                                          "  yellow                              125.                                                                               "                CH.sub.2CH.sub.2OCH.sub.3                                                                      CH.sub.3                                                                          "  yellow                              126.                                                                               "                                                                                                ##STR17##      CH.sub.3                                                                          "  yellow                              127.                                                                               "                CH.sub.2CH.sub.2CH.sub.2OCH.sub.3                                                              CH.sub.3                                                                          "  yellow                              128.                                                                               "                CH.sub.2CH.sub.2CH.sub.2OC.sub.2 H.sub.5                                                       CH.sub.3                                                                          "  yellow                              129.                                                                               4-Nitrophenyl    CH.sub.2CH.sub.2OH                                                                             CH.sub.3                                                                          "  scarlet                             130.                                                                               "                CH.sub.2CH.sub.2OCH.sub.3                                                                      CH.sub.3                                                                          "  scarlet                             131.                                                                               "                CH.sub.2CH.sub.2CH.sub.2OH                                                                     CH.sub.3                                                                          "  scarlet                             132.                                                                               "                CH.sub.2CH.sub.2CH.sub.2OCH.sub.3                                                              CH.sub.3                                                                          "  scarlet                             133.                                                                               "                CH.sub.2CH.sub.2CH.sub.2OC.sub.2 H.sub.5                                                       CH.sub.3                                                                          "  scarlet                             134.                                                                               2-Trifluoromethyl-4-chlorophenyl                                                                CH.sub.2C.sub.6 H.sub.5                                                                        CH.sub.3                                                                          "  yellow                              135.                                                                               "                CH.sub.2CH.sub.2CH.sub.2OH                                                                     CH.sub.3                                                                          "  yellow                              136.                                                                               "                CH.sub.2CH.sub.2CH.sub.2OCH.sub.3                                                              CH.sub.3                                                                          "  yellow                              137.                                                                               2-Cyano-5-chlorophenyl                                                                          CH.sub.2CH.sub.2OH                                                                             CH.sub.3                                                                          "  yellow                              138.                                                                               "                CH.sub.2CH.sub.2OCH.sub.3                                                                      CH.sub.3                                                                          "  yellow                              139.                                                                               "                CH.sub.2CH.sub.2CH.sub.2OH                                                                     CH.sub.3                                                                          "  yellow                              140.                                                                               "                                                                                                ##STR18##      CH.sub.3                                                                          "  yellow                              141.                                                                               "                CH.sub.2CH.sub.2CH.sub.2OC.sub.2 H.sub.5                                                       CH.sub.3                                                                          "  yellow                              142.                                                                               2-Chloro-4-nitrophenyl                                                                          CH.sub.2CH.sub.2OH                                                                             CH.sub.3                                                                          "  scarlet                             143.                                                                               "                CH.sub.2CH.sub.2OCH.sub.3                                                                      CH.sub.3                                                                          "  scarlet                             144.                                                                               "                CH.sub.2CH.sub.2CH.sub.2OH                                                                     CH.sub.3                                                                          "  scarlet                             145.                                                                               "                CH.sub.2CH.sub.2CH.sub.2OCH.sub.3                                                              CH.sub.3                                                                          "  scarlet                             146.                                                                               "                CH.sub.2CH.sub.2CH.sub.2OC.sub.2 H.sub.5                                                       CH.sub.3                                                                          "  scarlet                             147.                                                                               2-Methoxy-4-nitrophenyl                                                                         CH.sub.2CH.sub.2OH                                                                             CH.sub.3                                                                          "  red                                 148.                                                                               "                CH.sub.2CH.sub.2OCH.sub.3                                                                      CH.sub.3                                                                          "  red                                 149.                                                                               "                CH.sub.2CH.sub.2CH.sub.2OH                                                                     CH.sub.3                                                                          "  red                                 150.                                                                               "                CH.sub.2CH.sub.2CH.sub.2OCH.sub.3                                                              CH.sub.3                                                                          "  red                                 151.                                                                               "                CH.sub.2CH.sub.2CH.sub.2OC.sub.2 H.sub.5                                                       CH.sub.3                                                                          "  red                                 152.                                                                               2-Cyano-4-nitrophenyl                                                                           CH.sub.2CH.sub.2OH                                                                             CH.sub.3                                                                          "  red                                 153.                                                                               "                CH.sub.2CH.sub.2OCH.sub.3                                                                      CH.sub.3                                                                          "  red                                 154.                                                                               "                CH.sub.2CH.sub.2CH.sub.2OH                                                                     CH.sub.3                                                                          "  red                                 155.                                                                               2-Cyano-4-nitrophenyl                                                                            ##STR19##      CH.sub.3                                                                          "  red                                 156.                                                                               "                CH.sub.2CH.sub. 2CH.sub.2OCH.sub.3                                                             CH.sub.3                                                                          "  red                                 157.                                                                               "                CH.sub.2CH.sub.2CH.sub.2OC.sub.2 H.sub.5                                                       CH.sub.3                                                                          "  red                                 158.                                                                               2-Methylsulphonyl-4-nitrophenyl                                                                 CH.sub.2CH.sub.2OH                                                                             CH.sub.3                                                                          "  red                                 158.                                                                               "                CH.sub.2CH.sub.2OCH.sub.3                                                                      CH.sub.3                                                                          "  red                                 159.                                                                               "                CH.sub.2CH.sub.2CH.sub.2OH                                                                     CH.sub.3                                                                          "  red                                 160.                                                                               "                                                                                                ##STR20##      CH.sub.3                                                                          "  red                                 161.                                                                               "                CH.sub.2CH.sub.2CH.sub.2OCH.sub.3                                                              CH.sub.3                                                                          "  red                                 162.                                                                               "                CH.sub.2CH.sub.2CH.sub.2OC.sub.2 H.sub.5                                                       CH.sub.3                                                                          "  red                                 163.                                                                               2,5-Dimethoxy-4-nitrophenyl                                                                     CH.sub.2CH.sub.2OH                                                                             CH.sub.3                                                                          "  red                                 164.                                                                               "                CH.sub.2CH.sub.2OCH.sub.3                                                                      CH.sub.3                                                                          "  red                                 165.                                                                               "                CH.sub.2CH.sub.2CH.sub.2OH                                                                     CH.sub.3                                                                          "  red                                 166.                                                                               "                CH.sub.2CH.sub.2CH.sub.2OCH.sub.3                                                              CH.sub.3                                                                          "  red                                 167.                                                                               "                CH.sub.2CH.sub.2CH.sub.2OC.sub.2 H.sub.5                                                       CH.sub.3                                                                          "  red                                 168.                                                                               2,5-Diethoxy-4-nitrophenyl                                                                      CH.sub.2CH.sub.2OH                                                                             CH.sub.3                                                                          "  red                                 169.                                                                               "                CH.sub.2CH.sub.2OCH.sub.3                                                                      CH.sub.3                                                                          "  red                                 170.                                                                               2,5-Diethoxy-4-nitrophenyl                                                                      CH.sub.2CH.sub.2CH.sub.2OCH.sub.3                                                              CH.sub.3                                                                          "  red                                 171.                                                                               2-Carbomethoxy-4-nitrophenyl                                                                    CH.sub.2CH.sub.2OH                                                                             CH.sub.3                                                                          "  red                                 172.                                                                               "                CH.sub.2CH.sub.2OCH.sub.3                                                                      CH.sub.3                                                                          "  red                                 173.                                                                               "                CH.sub.2CH.sub.2CH.sub.2OH                                                                     CH.sub.3                                                                          "  red                                 174.                                                                               "                CH.sub.2CH.sub.2CH.sub.2OCH.sub.3                                                              CH.sub.3                                                                          "  red                                 175.                                                                               6-Methoxybenzthiazolyl-2                                                                        CH.sub.2CH.sub.2OH                                                                             CH.sub.3                                                                          "  scarlet                             176.                                                                               "                CH.sub.2CH.sub.2OCH.sub.3                                                                      CH.sub.3                                                                          "  scarlet                             177.                                                                               "                CH.sub.2CH.sub.2CH.sub.2OH                                                                     CH.sub.3                                                                          "  scarlet                             178.                                                                               "                CH.sub.2CH.sub.2CH.sub.2OCH.sub.3                                                              CH.sub.3                                                                          "  scarlet                             179.                                                                               6-Ethoxybenzthiazolyl-2                                                                         CH.sub.2CH.sub.2OCH.sub.3                                                                      CH.sub.3                                                                          "  scarlet                             180.                                                                               "                CH.sub.2CH.sub.2CH.sub.2OCH.sub.3                                                              "  "  scarlet                             181.                                                                               5,6-Dichlorobenzthiazolyl-2                                                                     CH.sub.2CH.sub.2OH                                                                             CH.sub.3                                                                          "  orange                              182.                                                                               "                CH.sub.2CH.sub.2OCH.sub.3                                                                      CH.sub.3                                                                          "  orange                              183 "                CH.sub.2CH.sub.2CH.sub.2OH                                                                     CH.sub.3                                                                          "  orange                              184.                                                                               "                CH.sub.2CH.sub.2CH.sub.2OCH.sub.3                                                              CH.sub.3                                                                          "  orange                              185.                                                                               "                CH.sub.2CH.sub.2CH.sub.2OC.sub.2 H.sub.5                                                       CH.sub.3                                                                          "  orange                              186.                                                                               5-Nitro-2,1-benzisothiazolyl-3                                                                  CH.sub.2CH.sub.2OH                                                                             CH.sub.3                                                                          "  blue                                187.                                                                               "                CH.sub.2CH.sub.2OCH.sub.3                                                                      CH.sub.3                                                                          "  blue                                188.                                                                               "                CH.sub.2CH.sub.2CH.sub.2OH                                                                     CH.sub.3                                                                          "  blue                                189.                                                                               "                CH.sub.2CH.sub.2CH.sub.2OCH.sub.3                                                              CH.sub.3                                                                          "  blue                                190.                                                                               "                CH.sub.2CH.sub.2CH.sub.2OC.sub.2 H.sub.5                                                       CH.sub.3                                                                          "  blue                                191.                                                                               1,3-Thiazolyl-2  CH.sub.2CH.sub.2OH                                                                             CH.sub.3                                                                          "  orange                              192.                                                                               "                CH.sub.2CH.sub.2CH.sub.2OCH.sub.3                                                              CH.sub.3                                                                          "  orange                              194.                                                                               3-Phenyl-1,2,4-thiadiazolyl-5                                                                   CH.sub.2CH.sub.2OH                                                                             CH.sub.3                                                                          "  orange                              195.                                                                               "                CH.sub.2CH.sub.2OCH.sub.3                                                                      CH.sub.3                                                                          "  orange                              196.                                                                               "                CH.sub.2CH.sub.2CH.sub.2OCH.sub.3                                                              CH.sub.3                                                                          "  orange                              197.                                                                               "                CH.sub.2CH.sub.2CH.sub.2OH                                                                     CH.sub.3                                                                          "  orange                              __________________________________________________________________________

If instead of the 3-cyanopyridine derivatives corresponding compounds substituted in the 3-position by carbonamide or carboxylic acid ester groups are used as coupling components, corresponding diazo components give dyestuffs which dye polyester materials in similar color and with similar fastness properties. 

We claim:
 1. A process for preparing an azo dyestuff comprisinga. reacting ##STR21## with at least two equivalents of R₃ NH₂ at a temperature of 110° to 130° C. to form ##STR22## b. and then coupling IV, V or VI with diazotized DNH₂ wherein V and VI are prepared by converting IV to ##STR23## by reaction at the cyano group; in which D is the radical of a diazo component; R is C₁ -C₆ -alkyl; C₁ -C₆ -alkyl substituted by halogen, CN, OH, C₁ -C₄ -alkoxy or C₂ -C₅ -alkoxycarbonyl; cyclohexyl; methyl-cyclohexyl; phenyl; phenyl substituted by C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, halogen or cyano; benzyl; phenethyl; or benzyl or phenethyl substituted with chlorine, C₁ -C₄ -alkyl or C₁ -C₄ -alkoxy; R₁ and Q₃ are independently C₁ -C₆ -alkyl; C₁ -C₆ -alkyl substituted with halogen, cyano, hydroxyl, C₁ -C₄ -alkoxy or C₂ -C₅ -alkoxycarbonyl; benzyl; phenethyl; benzyl or phenethyl substituted by chlorine, C₁ -C₄ -alkyl or C₁ -C₄ -alkoxy; Q₁ and Q₂ are independently of one another hydrogen, R or conjointly with the nitrogen atom form a morpholine, piperidine or pyrrolidine ring; and R₃ is C₁ -C₄ -alkyl; C₁ -C₄ -alkyl substituted by hydroxy, methoxy or ethoxy; benzyl; phenethyl; benzyl or phenethyl substituted by chlorine, C₁ -C₄ -alkyl or C₁ -C₄ -alkoxy; phenyl; or phenyl substituted by C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, halogen or cyano.
 2. Process of claim 1 in which R₃ NH₂ is a C₁ -C₄ -alkylamine; aniline; benzylamine; phenethylamine; γ-hydroxypropylamine, γ-ethoxypropylamine, β-methoxyethylamine or γ-methoxypropylamine.
 3. Process of claim 1 in which R₃ NH₂ is benzylamine.
 4. Process of claim 1 in which R₃ is benzyl.
 5. Process of claim 1 in which said azo dyestuff has the formula ##STR24##
 6. The process of claim 1 in which ##STR25## Y is halogen, nitro, cyano, CF₃, C₂ -C₅ -alkylcarbonylamino, C₁ -C₄ -alkylsulphonyl, C₂ -C₅ -alkoxycarbonyl, phenyl, ##STR26## Z is hydrogen, methyl, C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, nitrile or halogen;V₁ and V₂ independently of one another are hydrogen or C₁ -C₄ -alkyl; n is the number 1 or 2; R and R₁ are C₁ -C₆ -alkyl, or C₁ -C₆ -alkyl substituted by OH, CN, halogen, C₁ -C₄ -alkoxy or C₂ -C₅ -alkylcarbonyl; and Q₁ and Q₂ are hydrogen or C₁ -C₄ -alkyl.
 7. Process of claim 1 in which the cyano group is not converted;D is 4-methylsulphonylphenyl; R is CH₃ ; R₁ is CH₃ ; and R₃ is benzyl.
 8. Process of claim 1 in which the cyano group is not converted;D is 6-methoxybenzthiazolyl-2; R is CH₃ ; and R₃ is benzyl.
 9. Process of claim 1 in which the cyano group is not converted;D is 2,5-dichloro-4-sulphonamidophenyl; R is CH₃ ; R₁ is CH₃ ; and R₃ is --CH₂ --CH₂ --CH₂ OH.
 10. Process of claim 1 in which the cyano group is not converted:D is 2-cyano-4-nitrophenyl; R is --CH₃ ; R₁ is --CH₃ ; and R₃ is --CH₂ --CH₂ --CH₂ --O--C₂ H₅.
 11. Process of claim 1 in which the cyano group is not converted;D is 3-phenyl-1,2,4-thiadiazolyl-5; R is CH₃ ; R₁ is CH₃ ; and R₃ is --CH₂ --CH₂ --OH. 